Patent GB-737224-A (GB)
Title: Improvements in or relating to filaments, films and other shaped articles of cellulose esters
IPC: D01F2/28
Filed: 1953-06-25
Abstract: The dyeing and other properties of filaments, films and other shaped articles of unsaturated cellulose esters are improved by subjecting them to reaction with a permanganate salt.  The treatment improves the affinity of the articles for wool dyes and increases their resistance to the solvent action of organic liquids, particularly dry-cleaning liquids.  The reaction with a permanganate salt effects a cross-linking of molecular chains of the cellulose esters.  During the reaction, managanese dioxide is deposited on and is probably combined with the surfaces contacted by the permanganate to give them a dark colour.  The manganese dioxide may subsequently be removed chemically to provide a bleached surface suitable for dyeing, while retaining most of the properties of the dark material.  The cellulose ester may be an ester of an unsaturated dienoic acid such as vinyl acrylic, o-dihydrotoluic or sorbic acid, or it may be an ester of a simple unsaturated acid such as crotonic, acrylic, methacrylic or cinnamic acid.  The unsaturated acids may comprise the sole ester-forming substituents but preferably the cellulose ester is a mixed ester in which a saturated acyl group from an aliphatic acid forms the largest proportion of the ester substituents.  The degree of substitution in respect of the unsaturated acyl group is preferably in the range of 0.01 to 1.5.  The permanganate may be a sodium, potassium, calcium or zinc salt, and it may be used in concentrations of 0.01 per cent up to that of saturation in solution in water or aqueous solutions of organic solvents, e.g. aqueous acetone or isopropyl alcohol.  The temperature of treatment may be in the range of 0-100 DEG  C.  The shaped article containing and coloured by the manganese dioxide may be bleached to provide a dye-receptive surface by treating it with a reducing agent such as sulphurous acid, a sulphite, bisulphite, metabisulphite, hyposulphite, formaldehyde sulphoxylate, thiosulphate, formic acid or oxalic acid, and the treatment may be carried out at 20-100 DEG  C. The treatment with permanganate may be applied to filaments for use as paint brush bristles and in this case there is no need to remove the colouration due to the deposit of manganese dioxide.  In an example, an acetone-soluble cellulose acetate sorbate in the form of a film is immersed in a 50 per cent acetone solution containing 0.5 per cent of potassium permanganate for 5 minutes at 25 DEG  C.  The resultant dark brown film showed only 9 per cent solubility when immersed in acetone for 3 hours at 25 DEG  C.  In another example, cellulose acetate sorbate yarn is knitted to form a fabric and samples of the fabric are immersed in potassium permanganate solution at 25 DEG  C. for 2-5 minutes, and then bleached by soaking in a 5 per cent sodium bisulphite solution at 70 DEG  C.  The samples so treated have a reduced solubility in acetone and are insoluble in dry-cleaning solvents such as carbon tetrachloride, trichloroethylene and Stoddart solvent.  They are resistant to sticking when hot ironed and have improved receptivity for wool dyes such as Pontacyl Blue BL or Orange 2.  The dyeings are resistant to fading on exposure to acidic atmospheres.